Nonequilibrium Transition Research Articles

Transitions between equilibrium and nonequilibrium phenomena in the description of crystal growth

The close intertwining of equilibrium and nonequilibrium thermodynamic representations and transitions between the two limiting principles of thermodynamics: the second beginning and the principle of least coercion (minimum entropy production in the stationary regime) constitute the main content of phenomenological theories of crystal growth. The difference of basic postulates of two sections of thermodynamics forces to discuss problems of reversibility and irreversibility of time, scales of observed phenomena and rules of conjugation of thermodynamic forces and flows in theories of crystal growth. A variant of the solution of some conjugation problems is shown on the example of the fluctuation model of dislocation crystal growth, which is based on the stationary isothermal process of thermodynamic free energy fluctuations. In the case of the limiting mode of adsorption of impurities on the crystal face according to the Langmuir model, the free energy fluctuations possessing the absence of the memory effect allow us to identify three chemical potentials of building particles that determine the corresponding values of solution supersaturations realized at different scale levels at the growing crystal face containing a helical dislocation. The supersaturations control quasi-equilibrium and nonequilibrium thermodynamic processes that constitute a single dislocation mechanism of crystal growth.

Nonequilibrium Transition between Dissipative Time Crystals

We show a dissipative phase transition in a driven nonlinear quantum oscillator in which a discrete time-translation symmetry is spontaneously broken in two different ways. The corresponding regimes display either discrete or incommensurate time-crystal order, which we analyze numerically and analytically beyond the classical limit, addressing observable dynamics, phenomenology in different (laboratory and rotating) frames, Liouvillian spectral features, and quantum fluctuations. Via an effective semiclassical description, we show that phase diffusion dominates in the incommensurate time crystal (or continuous time crystal in the rotating frame), which manifests as a band of eigenmodes with a lifetime growing linearly with the mean-field excitation number. Instead, in the discrete time-crystal phase, the leading fluctuation process corresponds to quantum activation with a single mode that has an exponentially growing lifetime. Interestingly, the transition between these two regimes manifests itself already in the quantum regime as a spectral singularity, namely, as an exceptional point mediating between phase diffusion and quantum activation. Finally, we discuss this transition between different time-crystal orders in the context of synchronization phenomena. Published by the American Physical Society 2024

Information cascade on networks and phase transitions

Herein, we consider a voting model for information cascades on several types of networks – a random graph, the Barabási–Albert(BA) model, and lattice networks – by using one parameter ω; ω=1,0,−1 respectively correspond to these networks. Our objective is to study the relation between the phase transitions and networks using the parameter, ω which is related to the size of hubs. We discuss the differences between the phases in which the networks depend. In ω≠−1, without a lattice, the following two types of phase transitions can be observed: information cascade transition and super-normal transition. The first is the transition between a state where most voters make correct choices and a state where most of them are wrong. This is an absorption transition that belongs to the non-equilibrium transition. In the symmetric case, the phase transition is continuous and the universality class is the same as nonlinear Pólya model. In contrast, in the asymmetric case, there is a discontinuous phase transition, where the gap depends on the network. As ω increases, the size of the hub and the gap increase. Therefore, a network that has hubs has a greater effect through this phase transition. The critical point of information cascade transition does not depend on ω. The super-normal transition is the transition of the convergence speed, and the critical point of the convergence speed transition depends on ω. At ω=1, in the BA model, this transition disappears, and the range where we can observe the phase transition is the same as that in the percolation model on the network. Both phase transitions disappear at ω=−1 in the lattice case. In conclusion, as the performance near the lattice case, ω∼−1 exhibits the best performance of the voting in all networks. As the hub size decreases, the performance improves. Finally, we show the relation between the voting model and the elephant walk model.

Microscopic pathways of transition from low-density to high-density amorphous phase of water.

In recent years, much attention has been devoted to understanding the pathways of phase transition between two equilibrium condensed phases (such as liquids and solids). However, the microscopic pathways of transition involving non-equilibrium, non-diffusive amorphous (glassy) phases still remain poorly understood. In this work, we have employed computer simulations, persistence homology (a tool rooted in topological data analysis), and machine learning to probe the microscopic pathway of pressure-induced non-equilibrium transition between the low- and high-density amorphous (LDA and HDA, respectively) ice phases of the TIP4P/2005 and ST2 water models. Using persistence homology and machine learning, we introduced a new order parameter that unambiguously identifies the LDA- and HDA-like local environments. The LDA phase transitions continuously and collectively into the corresponding HDA phase via a pre-ordered intermediate phase during the isothermal compression. The local order parameter susceptibilities show a maximum near the transition pressure (P*)-suggesting maximum structural heterogeneities near P*. The HDA-like clusters are structurally ramified and spatially delocalized inside the LDA phase near the transition pressure. We also found manifestations of the first-order low-density to high-density liquid transition in the sharpness of the order parameter change during the LDA to HDA transition. We further investigated the (geometrical) structures and topologies of the LDA and HDA ices formed via different protocols and also studied the dependence of the (microscopic) pathway of phase transition on the protocol followed to prepare the initial LDA phase. Finally, the method adopted here to study the phase transition pathways is not restricted to the system under consideration and provides a robust way of probing phase transition pathways involving any two condensed phases at both equilibrium and out-of-equilibrium conditions.

Correlation-driven nonequilibrium exciton site transition in a WSe2/WS2 moiré supercell

Moiré superlattices of transition metal dichalcogenides offer a unique platform to explore correlated exciton physics with optical spectroscopy. Whereas the spatially modulated potentials evoke that the exciton resonances are distinct depending on a site in a moiré supercell, there have been no clear demonstration how the moiré excitons trapped in different sites dynamically interact with the doped carriers; so far the exciton-electron dynamic interactions were presumed to be site-dependent. Thus, the transient emergence of nonequilibrium correlations are open questions, but existing studies are limited to steady-state optical measurements. Here we report experimental fingerprints of site-dependent exciton correlations under continuous-wave as well as ultrashort optical excitations. In near-zero angle-aligned WSe2/WS2 heterobilayers, we observe intriguing polarization switching and strongly enhanced Pauli blocking near the Mott insulating state, dictating the dominant correlation-driven effects. When the twist angle is near 60°, no such correlations are observed, suggesting the strong dependence of atomic registry in moiré supercell configuration. Our studies open the door to largely unexplored nonequilibrium correlations of excitons in moiré superlattices.

Bowtie design for thermal expansion mimicry and mitigation

A geometric bowtie design for the purpose of mimicking (matching) and/or mitigating (reducing) the thermal expansion effects between two laterally opposing structures is investigated. A bowtie design is that of two opposing overlapping triangles with farthest sides parallel. This design embodies thermal centering concepts which utilize the relationships of the trigonometric identity known as the law of sines for a triangle from which beneficial thermal properties can be engineered. For validation. The bowtie design is embodied using two separated Zerodur plane mirrors, symmetrically opposed, and each seated in Maxwell-style kinematic couplings of spheres and vee-groves. The vee-grooves form a wheel-like pattern on an aluminum baseplate. The intersection of the vee-grooves is the common overlapping thermal center of both mirror mounts. The refractive-index corrected interferometric measurement of the displacement between these two mirrors shows that even during non-isothermal non-equilibrium transitions and states, the nominal ∼90 μm thermally induced (13 °C) expansion of an aluminum baseplate can be mitigated, being reduced more than 98 % to ∼1.4 μm by mimicking the thermal expansion properties of the mirrors’ structural material. Engineering thermally-invariant kinematic bowtie designs using materials having higher thermal expansion coefficients is also described.

Effects of gas velocity on nonequilibrium characteristics of fluidization

The gas velocity is a key factor of the macroscale operating conditions, affecting the nonequilibrium behavior and regime transitions of fluidization, but the mechanism of its effects remains unclear, resulting in a deterioration of the accuracy of the two-fluid model (TFM) simulation with the increase of the gas velocity. To seek its underlying mechanism, we performed time-resolved, particle-tracking velocimetry (PTV) measurements of a fluidized bed operated under bubbling to turbulent states, thereon the analysis of the probability density distribution of particle velocity, and hydrodynamic parameters. It is found that a stronger nonequilibrium exists with the increase of the gas velocity, in the sense that the bimodal distribution of particle velocity is more significant at turbulent fluidization. The total fluctuating energy and stress show a scale separation, suggesting that a reasonable continuum modeling should take into account the whole range of fluctuation.

Real-time dynamics of false vacuum decay

We investigate false vacuum decay of a relativistic scalar field initialized in the metastable minimum of an asymmetric double-well potential. The transition to the true ground state is a well-defined initial-value problem in real time, which can be formulated in nonequilibrium quantum field theory on a closed time path. We employ the nonperturbative framework of the two-particle irreducible (2PI) quantum effective action at next-to-leading order in a large-N expansion. We also compare to classical-statistical field theory simulations on a lattice in the high-temperature regime. By this, we demonstrate that the real-time decay rates are comparable to those obtained from the conventional Euclidean (bounce) approach. In general, we find that the decay rates are time dependent. For a more comprehensive description of the dynamics, we extract a time-dependent effective potential, which becomes convex during the nonequilibrium transition process. By solving the quantum evolution equations for the one- and two-point correlation functions for vacuum initial conditions, we demonstrate that quantum corrections can lead to transitions that are not captured by classical-statistical approximations. Published by the American Physical Society 2024

X-ray-induced piezoresponse during X-ray photon correlation spectroscopy of PbMg1/3Nb2/3O3.

X-ray photon correlation spectroscopy (XPCS) holds strong promise for observing atomic-scale dynamics in materials, both at equilibrium and during non-equilibrium transitions. Here an in situ XPCS study of the relaxor ferroelectric PbMg1/3Nb2/3O3 (PMN) is reported. A weak applied AC electric field generates strong response in the speckle of the diffuse scattering from the polar nanodomains, which is captured using the two-time correlation function. Correlated motions of the Bragg peak are also observed, which indicate dynamic tilting of the illuminated volume. This tilting quantitatively accounts for the observed two-time speckle correlations. The magnitude of the tilting would not be expected solely from the modest applied field, since PMN is an electrostrictive material with no linear strain response to the field. A model is developed based on non-uniform static charging of the illuminated surface spot by the incident micrometre-scale X-ray beam and the electrostrictive material response to the combination of static and dynamic fields. The model qualitatively explains the direction and magnitude of the observed tilting, and predicts that X-ray-induced piezoresponse could be an important factor in correctly interpreting results from XPCS and nanodiffraction studies of other insulating materials under applied AC field or varying X-ray illumination.

Abnormal blockage of water flow in valveless nanopumps

In the narrow orifice of a cone-shaped channel, blockage can occur for granular matter. However, water molecules can enter into and even permeate through carbon nanotubes of diameters down to 0.8 nm at ultrafast rates. Here we demonstrate by molecular dynamics simulations that clogging can also emerge unexpectedly in the water flowing through a nanoscale valve-less pump. The designed pump features two truncated carbon nanocones, with the narrowest region having a diameter of 1.2 nm (larger than that of (6, 6) carbon nanotube), linked to a fluid cavity volume, and is powered by the vibration of a graphene sheet. In the low frequency range, water molecules can be driven through the nanocones effectively by the vibration of the graphene sheet. The maximum flux reaches 83 ns<sup>–1</sup>, which is approximately 20 times the measured value of (3.9 ± 0.6) ns<sup>–1</sup> for aquaporin-1. However, at higher frequencies, water molecules suffer blockage at the narrow exits. Much unlike granular matter, high-frequency vibration cannot restore water flow. The key to this phenomenon is that in the narrow exits of two nanocones acting as diffuser/nozzle, the number density of water molecules rapidly increases with frequency increasing, the tight hydrogen-bonding network is formed, and the mean lifetime of hydrogen bonds increases dramatically under high-frequency vibrations. High frequency fluctuations in the middle chamber make H-bond network between water molecules in the narrow exits more stable. The probability density distribution of water exhibits a non-equilibrium transition from a disordered state to ordered state. This work reveals a new mechanism of water flowing/blocking in a nanoscale valve-less pump based on two asymmetrical nanocones, offers valuable insights into understanding nonequilibrium jamming transition in nanoscale fluid.

Steady-state thermodynamics of a system with heat and mass flow coupling.

Equilibrium thermodynamics describes the energy exchange of a body with its environment. Here, we describe the global energy exchange of an ideal gas in the Coutte flow in a thermodynamic-like manner. We derive a fundamental relation between internal energy as a function of parameters of state. We analyze a non-equilibrium transition in the system and postulate the extremum principle, which determines stable steady states in the system. The steady-state thermodynamic framework resembles equilibrium thermodynamics.

Comparison of Equilibrium and Nonequilibrium Approaches for Relative Binding Free Energy Predictions.

Alchemical relative binding free energy calculations have recently found important applications in drug optimization. A series of congeneric compounds are generated from a preidentified lead compound, and their relative binding affinities to a protein are assessed in order to optimize candidate drugs. While methods based on equilibrium thermodynamics have been extensively studied, an approach based on nonequilibrium methods has recently been reported together with claims of its superiority. However, these claims pay insufficient attention to the basis and reliability of both methods. Here we report a comparative study of the two approaches across a large data set, comprising more than 500 ligand transformations spanning in excess of 300 ligands binding to a set of 14 diverse protein targets. Ensemble methods are essential to quantify the uncertainty in these calculations, not only for the reasons already established in the equilibrium approach but also to ensure that the nonequilibrium calculations reside within their domain of validity. If and only if ensemble methods are applied, we find that the nonequilibrium method can achieve accuracy and precision comparable to those of the equilibrium approach. Compared to the equilibrium method, the nonequilibrium approach can reduce computational costs but introduces higher computational complexity and longer wall clock times. There are, however, cases where the standard length of a nonequilibrium transition is not sufficient, necessitating a complete rerun of the entire set of transitions. This significantly increases the computational cost and proves to be highly inconvenient during large-scale applications. Our findings provide a key set of recommendations that should be adopted for the reliable implementation of nonequilibrium approaches to relative binding free energy calculations in ligand-protein systems.

Transition Time Determination of Single-Molecule FRET Trajectories via Wasserstein Distance Analysis in Steady-State Variations in smFRET (WAVE).

Many biological molecules respond to external stimuli that can cause their conformational states to shift from one steady state to another. Single-molecule FRET (Fluorescence Resonance Energy Transfer) is of particular interest to not only define the steady-state conformational ensemble usually averaged out in the ensemble of molecules but also characterize the dynamics of biomolecules. To study steady-state transitions, i.e., non-equilibrium transitions, a data analysis methodology is necessary to analyze single-molecule FRET photon trajectories, which contain mixtures of contributions from two steady-state statuses and include non-equilibrium transitions. In this study, we introduce a novel methodology called WAVE (Wasserstein distance Analysis in steady-state Variations in smFRET) to detect and locate non-equilibrium transition positions in FRET trajectories. Our method first utilizes a combined STaSI-HMM (Stepwise Transitions with State Inference Hidden Markov Model) algorithm to convert the original FRET trajectories into discretized trajectories. We then apply Maximum Wasserstein Distance analysis to differentiate the FRET state compositions of the fitting trajectories before and after the non-equilibrium transition. Forward and backward algorithms, based on the Minimum Description Length (MDL) principle, are used to find the refined positions of the non-equilibrium transitions. This methodology allows us to observe changes in experimental conditions in chromophore-tagged biomolecules or vice versa.

Nonequilibrium warm dense matter investigated with laser-plasma-based XANES down to the femtosecond.

The use of laser-plasma-based x-ray sources is discussed, with a view to carrying out time-resolved x-ray absorption spectroscopy measurements, down to the femtosecond timescale. A review of recent experiments performed by our team is presented. They concern the study of the nonequilibrium transition of metals from solid to the warm dense regime, which imposes specific constraints (the sample being destroyed after each shot). Particular attention is paid to the description of experimental devices and methodologies. Two main types of x-ray sources are compared, respectively, based on the emission of a hot plasma, and on the betatron radiation from relativistic electrons accelerated by laser.

Yielding under compression and the polyamorphic transition in silicon

We investigate the behavior of amorphous silicon under hydrostatic compression using molecular simulations. During compression, amorphous silicon undergoes a discontinuous nonequilibrium transition from a low-density to a high-density structure at a pressure of around $13$-$16$~GPa. Ensemble-averaged density and elastic constants change discontinuously across the transition. Densification of individual glassy samples occurs through a series of discrete plastic events, each of which is accompanied by a vanishing shear modulus. This is the signature of a series of elastic instabilities, similar to shear transformation zones observed during shear yielding of glasses. We compare the structure obtained during compression with a near-equilibrium form of amorphous silicon obtained by quenching a melt at constant pressure. This gives structures identical to nonequilibrium compression at low and high pressure, but the transition between them occurs gradually rather than discontinuously. Our observations indicate that the polyamorphic transition is of a nonequilibrium nature, and it has the characteristics of a yield transition that occurs under compression instead of shear.

Crafting the dynamical structure of synchronization by harnessing bosonic multilevel cavity QED

Many-body cavity QED experiments are established platforms to tailor and control the collective responses of ensembles of atoms, interacting through one or more common photonic modes. The rich diversity of dynamical phases they can host, calls for a unified framework. Here we commence this program by showing that a cavity QED simulator assembled from $N$-levels bosonic atoms, can reproduce and extend the possible dynamical responses of collective observables occurring after a quench. Specifically, by initializing the atoms in classical or quantum states, or by leveraging intra-levels quantum correlations, we craft on demand the entire synchronization/desynchronization dynamical crossover of an exchange model for $SU(N)$ spins. We quantitatively predict the onset of different dynamical responses by combining the Liouville-Arnold theorem on classical integrability with an ansatz for reducing the collective evolution to an effective few-body dynamics. Among them, we discover a synchronized chaotic phase induced by quantum correlations and associated to a first order non-equilibrium transition in the Lyapunov exponent of collective atomic dynamics. Our outreach includes extensions to other spin-exchange quantum simulators and a universal conjecture for the dynamical reduction of non-integrable all-to-all interacting systems.

Fluctuations of heat in driven two-state systems: Application to a single-electron box with superconducting gap.

By using trajectory averaging to analyze the statistics of energy dissipation in the nonequilibrium energy-state transitions of a driven two-state system, we show that the average energy dissipation induced by external driving is connected to its fluctuations about equilibrium through the simple relation 2k_{B}T〈Q〉=〈δQ^{2}〉, which is preserved by an adiabatic approximation scheme. We use this scheme to obtain the heat statistics of a single-electron box with a superconducting lead in the slow-driving regime, where the dissipated heat becomes normally distributed with a relatively high probability to be extracted from the environment rather than dissipated. We also discuss the validity of heat fluctuation relations beyond driven two-state transitions and the slow-driving regime.

Order-disorder transition in the zero-temperature Ising model on random graphs.

The zero-temperature Ising model is known to reach a fully ordered ground state in sufficiently dense random graphs. In sparse random graphs, the dynamics gets absorbed in disordered local minima at magnetization close to zero. Here, we find that the nonequilibrium transition between the ordered and the disordered regime occurs at an average degree that slowly grows with the graph size. The system shows bistability: The distribution of the absolute magnetization in the reached absorbing state is bimodal, with peaks only at zero and unity. For a fixed system size, the average time to absorption behaves nonmonotonically as a function of average degree. The peak value of the average absorption time grows as a power law of the system size. These findings have relevance for community detection, opinion dynamics, and games on networks.

Rheological signatures of a glass-glass transition in an aging colloidal clay

The occurrence of non-equilibrium transitions between arrested states has recently emerged as an intriguing issue in the field of soft glassy materials. The existence of one such transition has been suggested for aging colloidal clays (Laponite® suspensions) at a weight concentration of 3.0%, although further experimental evidences are necessary to validate this scenario. Here, we test the occurrence of this transition for spontaneously aged (non-rejuvenated) samples by exploiting the rheological tools of dynamical mechanical analysis. On imposing consecutive compression cycles to differently aged clay suspensions, we find that quite an abrupt change of rheological parameters occurs for ages around three days. For Young’s and elastic moduli, the change with the waiting time is essentially independent from the deformation rate, whereas other “fluid-like” properties, such as the loss modulus, do clearly display some rate dependence. We also show that the crossover identified by rheology coincides with deviations of the relaxation time (obtained through x-ray photon correlation spectroscopy) from its expected monotonic increase with aging. Thus, our results robustly support the existence of a glass-glass transition in aging colloidal clays, highlighting characteristic features of their viscoelastic behavior.

Estimation of non-equilibrium transition rate from gene expression data.

The dynamical properties of many complex physical and biological systems can be quantified from the energy landscape theory. Previous approaches focused on estimating the transition rate from landscape reconstruction based on data. However, for general non-equilibrium systems (such as gene regulatory systems), both the energy landscape and the probability flux are important to determine the transition rate between attractors. In this work, we proposed a data-driven approach to estimate non-equilibrium transition rate, which combines the kernel density estimation and non-equilibrium transition rate theory. Our approach shows superior performance in estimating transition rate from data, compared with previous methods, due to the introduction of a nonparametric density estimation method and the new saddle point by considering the effects of flux. We demonstrate the practical validity of our approach by applying it to a simplified cell fate decision model and a high-dimensional stem cell differentiation model. Our approach can be applied to other biological and physical systems.